NO150971B - PROCEDURE FOR CLEANING OF CONDENSATIVES FROM THE SULPHATE PROCESS - Google Patents
PROCEDURE FOR CLEANING OF CONDENSATIVES FROM THE SULPHATE PROCESS Download PDFInfo
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- NO150971B NO150971B NO811259A NO811259A NO150971B NO 150971 B NO150971 B NO 150971B NO 811259 A NO811259 A NO 811259A NO 811259 A NO811259 A NO 811259A NO 150971 B NO150971 B NO 150971B
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- condensates
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- compounds
- evaporation
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- 238000000034 method Methods 0.000 title claims description 28
- 230000008569 process Effects 0.000 title claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims description 14
- 229910021653 sulphate ion Inorganic materials 0.000 title claims description 11
- 238000004140 cleaning Methods 0.000 title claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000004581 coalescence Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 16
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 14
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 13
- 238000001704 evaporation Methods 0.000 description 13
- 230000008020 evaporation Effects 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 238000010411 cooking Methods 0.000 description 5
- 229920001021 polysulfide Polymers 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 238000003918 potentiometric titration Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000004133 Sodium thiosulphate Substances 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 241000779819 Syncarpia glomulifera Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000019988 mead Nutrition 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000036284 oxygen consumption Effects 0.000 description 2
- 239000001739 pinus spp. Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 229940036248 turpentine Drugs 0.000 description 2
- 241000972773 Aulopiformes Species 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 241001520316 Phascolarctidae Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- -1 methanol Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- HEDOODBJFVUQMS-UHFFFAOYSA-N n-[2-(5-methoxy-1h-indol-3-yl)ethyl]-n-methylpropan-2-amine Chemical compound COC1=CC=C2NC=C(CCN(C)C(C)C)C2=C1 HEDOODBJFVUQMS-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000011045 prefiltration Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Chemical class 0.000 description 1
- 229920005989 resin Chemical class 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 235000019515 salmon Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000820 toxicity test Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/06—Treatment of pulp gases; Recovery of the heat content of the gases; Treatment of gases arising from various sources in pulp and paper mills; Regeneration of gaseous SO2, e.g. arising from liquors containing sulfur compounds
- D21C11/08—Deodorisation ; Elimination of malodorous compounds, e.g. sulfur compounds such as hydrogen sulfide or mercaptans, from gas streams
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/0057—Oxidation of liquors, e.g. in order to reduce the losses of sulfur compounds, followed by evaporation or combustion if the liquor in question is a black liquor
Landscapes
- Treating Waste Gases (AREA)
- Paper (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Description
Foreliggende oppfinnelse vedrører en fremgangsmåte av den The present invention relates to a method thereof
art som er angitt i krav l's ingress. species specified in claim l's preamble.
Ved fremstilling av cellulose etter sulfatprosessen behandles fiber råstoff et (vanligvis trevirke i form av flis) under hoyt trykk og temperatur med den såkalte hvitlut, der de aktive kjemikaliene består av natriumhydroksyd og natrium sulfid (1,2 ). Dessuten anvender endel fabrikker tilleggs - kjemikalier, som polysulfid o.a. In the production of cellulose after the sulphate process, a fibrous raw material (usually wood in the form of chips) is treated under high pressure and temperature with the so-called white liquor, where the active chemicals consist of sodium hydroxide and sodium sulphide (1,2 ). In addition, some factories use additional chemicals, such as polysulphide and others.
Etter kokeprosessens avslutning skilles fibermaterialet (sulfatcellulosen After the cooking process is finished, the fibrous material (the sulphate cellulose
eller sulfatmassen) fra det utloste, opploste organiske materialet og de uorganiske kjemikaliene. P.g.a. sin farge kalles væskefasen nå for svartlut. Svartluten konsentreres til så hoyt torrstoffinnhold at den kan brennes. Derved får man frigitt varme (evt. også el. kraft) samt uorganiske kjemikalier som kan omformes til hvitlutkjemikalier, noe som er en absolutt nodvendighet for prosessens okonomi. Endel flyktige forbindelser (terpentin, metanol o.a. ) og luft tas ut fra kokeren separat eller utskilles fra svart- or the sulphate mass) from the leached, dissolved organic material and the inorganic chemicals. Because of. its color, the liquid phase is now called black liquor. The black liquor is concentrated to such a high dry matter content that it can be burned. This releases heat (possibly also electric power) as well as inorganic chemicals that can be transformed into white liquor chemicals, which is an absolute necessity for the economy of the process. Some volatile compounds (turpentine, methanol, etc.) and air are removed from the boiler separately or separated from black
luten idet denne utsettes for redusert trykk (i forhold til koke r trykket). the lye as it is exposed to reduced pressure (compared to the boiling pressure).
Etter avkjoling vil endel av disse folge den vanndamp som kondenseres. After cooling, some of these will follow the water vapor that is condensed.
Den ikke-vannloselige fase benevnes gjerne sulfatterpentin. Kondensatene The non-water-soluble phase is often referred to as sulphate turpentine. The condensates
fra denne del av prosessen benevnes gjerne som kokerikondensat. from this part of the process is often referred to as cooking condensate.
Konsentreringen av svartluten (inkl. vaskevannet fra fortrengning av denne The concentration of the black liquor (incl. the washing water from its displacement
fra cellulosen) utfores vanligvis i et flertrinns inndampningsanlegg, til dels under vakuum. Avdampet vann fåes ut i form av kondensater. Sammen med evt. vann f ra anleggets vakuumpumpe o.a. benevnes utgående vann herfra som inndampningskondensater. Bortsett fra den del som stammer fra indirekte oppvarming med fxiskdamp, er også inndampningskondensatene mer eller mindre forurenset. from the cellulose) is usually carried out in a multi-stage evaporation plant, partly under vacuum. Evaporated water is obtained in the form of condensates. Together with any water from the plant's vacuum pump, etc. outgoing water from here is referred to as evaporation condensates. Apart from the part that originates from indirect heating with fxic steam, the evaporation condensates are also more or less contaminated.
Enkelte fabrikker utnytter endel av dampen fra kokeprosessen til en for-inndampning av svartluten. Slike f or- inndampningskondensater kan betraktes som en mellomting mellom kokeri - og inndampningskondensater. De ulike avdragsdamp- og kondensattyper kan i det hele tatt være sammenknyttet på forskjellig måte i prosessen, noe som imidlertid ikke ansess å være av betydning i denne forbindelse. Certain factories utilize part of the steam from the boiling process for a pre-evaporation of the black liquor. Such pre-evaporation condensates can be regarded as a middle ground between cooking and evaporation condensates. The different steam and condensate types may in general be connected in different ways in the process, which, however, is not considered to be of importance in this connection.
Fra svartluten utskilles en såpe (sulfatsåpe). Denne består vesentlig av forsåpede fettsyrer og harpikssyrer (abietinsyrer), men inneholder også uforsåpede forbindelser. Såpen tas vanligvis vare på, og den omformes da gjerne til såkalt tallolje. Også inndampningskondensatene vil inneholde mer eller mindre finfordelt "olje", dvs. en vannutloselig fase, noe som vil være en ulempe ved enhver videre behandling av dem. A soap (sulphate soap) is separated from the black liquor. This mainly consists of saponified fatty acids and resin acids (abietic acids), but also contains unsaponified compounds. The soap is usually taken care of, and it is then often transformed into so-called tallow oil. The evaporation condensates will also contain more or less finely divided "oil", i.e. a water-insoluble phase, which will be a disadvantage in any further treatment of them.
De her nevnte kondensater har det til felles at de inneholder diverse flyktige stoffer, hvorav endel er lavere svovelholdige forbindelser. Særlig under inndampningen avgår det illeluktende og giftige gasser, som hydrogen- The condensates mentioned here have in common that they contain various volatile substances, some of which are lower sulfur compounds. Particularly during evaporation, foul-smelling and toxic gases, such as hydrogen
sulfid (H-jS), metylmerkaptan (CH^SH) og lignende fra svartluten, hvorav sulphide (H-jS), methyl mercaptan (CH^SH) and the like from the black liquor, of which
en ikke uvesentlig del vil gjenfinnes i kondensatene. Kondensatene er derfor illeluktende og toksiske. a not insignificant part will be found in the condensates. The condensates are therefore foul-smelling and toxic.
Innholdet av metanol o.a. betyr at utslipp av kondensater vil medfore en belastning på resipienten i form av opplost organisk materiale med til - horende kjemisk oksygenforbruk (COD) og biokjemisk oksygenforbruk (BOD). De tre forhold, lukt, toksisitet overfor akvatisk liv samt organisk belast- The content of methanol and other means that the discharge of condensates will cause a burden on the recipient in the form of dissolved organic material with associated chemical oxygen consumption (COD) and biochemical oxygen consumption (BOD). The three conditions, smell, toxicity to aquatic life and organic load
ning, betyr at sulfatprosessens kondensater representerer et alvorlig miljoproblem. Samtidig begrenses også anvendelsesmulighetene av urensede kondensater som væskekilde innen prosessen ved deres avgivning av giftige og illeluktende gasser samt deres innhold av finfordelte oljer. ning, means that the sulfate process condensates represent a serious environmental problem. At the same time, the application possibilities of uncleaned condensates as a liquid source within the process are also limited by their emission of toxic and malodorous gases as well as their content of finely divided oils.
De metoder som idag benyttes for rensing av sulfatprosessens kondensater, The methods that are currently used for cleaning the sulfate process condensates,
er forst og fremst basert på avdriving av flyktige forbindelser ( der iblandt metanol og illeluktende stoffer) ved hjelp av damp eller luft (stripping) (2 a, 2 b). De avdrevne gasser/damper går gjerne til destruksjon ved forbrenning, sammen med endel ukondenserbare gasser fra koke- og gjenvinnings - prosessen. is primarily based on the removal of volatile compounds (including methanol and malodorous substances) using steam or air (stripping) (2 a, 2 b). The expelled gases/vapours are usually destroyed by combustion, together with some non-condensable gases from the cooking and recovery process.
En renseprosess basert på nedbrytning ved hjelp av mikro-organismer blir også benyttet ( 3 ). A cleaning process based on decomposition using micro-organisms is also used ( 3 ).
Foreliggende fremgangsmåte tar sikte på å fjerne kon- The present method aims to remove con-
densatenes illeluktende stoffer ved hjelp av kombinert oksydasjon og adsorpsjon etter en forutgående fjerning av finfordelt olje bl. a. ved hjelp av koalesens, når dette er påkrevet. Et lite f or soksanlegg har i et par år vært provet ved en sulfatfabrikk for studie av ulike kondensattyper, katalysa-tortyper, levetid og regenereringsmuligheter for katalysatoren osv. the densat's malodorous substances by means of combined oxidation and adsorption after a prior removal of finely divided oil, e.g. a. by means of coalescence, when this is required. For a couple of years, a small pilot plant has been tested at a sulphate factory for the study of different condensate types, catalyst types, lifetime and regeneration possibilities for the catalyst, etc.
Det er kjent at hydrogensulfidgass i luft oksyderes på en egnet katalysator, som f. eks. aktivt kull. Ved denne gassreaksjon omdannes H£S til elementært svovel. Prosessen kan fores videre til svoveldioksyd (SO2), som jo også (sammen med noe SO3) er sluttproduktet ved forbrenning av H2S, It is known that hydrogen sulphide gas in air is oxidized on a suitable catalyst, such as e.g. activated charcoal. In this gas reaction, H£S is converted into elemental sulphur. The process can be carried on to sulfur dioxide (SO2), which is also (along with some SO3) the end product of the combustion of H2S,
svovel og mange andre svovelforbindelser. Det har også vært foreslått å rense illelukktende gasser ved hjelp av alkali og aktivt kull. sulfur and many other sulfur compounds. It has also been proposed to purify foul-smelling gases using alkali and activated carbon.
Hydrogensulfid er loselig i alkali, f. eks. i natronlut, ved at det dannes sulfider (NaHS og/eller Na2S i NaOH). I sulfatprosessens meget sterkt basiske hvitlut er, som nevnt, natriumhydr oksyd og natrium sulfid de aktive koke-kjemikalier. Slik hvitlut oksyderes langsomt av luft, og oksydasjons-produktene vil være natrium sulfitt, natriumtiosulf at og natrium sulfat. Hydrogen sulfide is soluble in alkali, e.g. in caustic soda, by the formation of sulphides (NaHS and/or Na2S in NaOH). In the sulphate process' very strongly basic white liquor, as mentioned, sodium hydroxide and sodium sulphide are the active cooking chemicals. Such white liquor is slowly oxidized by air, and the oxidation products will be sodium sulphite, sodium thiosulphate and sodium sulphate.
Ved tilstedeværelse av egnet oksygenoverforer eller katalysator kan oksydasjonstiden reduseres betraktelig, og det dannes natriumpolysulfid og natriumtiosulf at. Som eksempel kan nevnes innblanding av en viss del svartlut (PFI-patent) eller bruk av en spesiell katalysatormasse (Meads Moxyprosess) ( 4, 5 ). In the presence of a suitable oxygen transfer agent or catalyst, the oxidation time can be reduced considerably, and sodium polysulphide and sodium thiosulphate are formed. Examples include the mixing of a certain amount of black liquor (PFI patent) or the use of a special catalyst mass (Meads Moxyprocess) ( 4, 5 ).
Aktivt kull er alminnelig kjent innen renseteknikk for fjerning av små mengder forurensninger. Dette er basert på stoffets store indre overflate. Overflaten vil blokkeres av de adsorberte stoffer, slik at en eller annen Activated carbon is commonly known in cleaning technology for the removal of small amounts of pollutants. This is based on the fabric's large internal surface. The surface will be blocked by the adsorbed substances, so that one or the other
form for regenerering vil være påkrevet dersom det er snakk om storre mengder forururensninger. some form of regeneration will be required if there is a question of large amounts of pollution.
Foreliggende fremgangsmåte er særpreget ved det som er angitt i krav r-s karakteriserende del. The present method is characterized by what is stated in the characterizing part of claim r.
FORSØK ATTEMPT
Forurensede, illeluktende kondensater fra en sulfatfabrikk er sammen med luft ledet gjennom en kolonne fylt med aktivt kull. Contaminated, foul-smelling condensates from a sulphate factory are, together with air, passed through a column filled with activated carbon.
Innledende forsok viste at Initial trials showed that
1) Lukten ble fjernet ved behandlingen. 1) The smell was removed by the treatment.
2) Hydrogensulfid og metylmerkaptan ble fjernet (vist ved potensio-metriske titreringer). 3) Lukt, hydrogensulfid og metylmerkaptan ble ikke fjernet hvis det ikke gikk tilstrekkelig luft sammen med væsken. 2) Hydrogen sulphide and methyl mercaptan were removed (shown by potentiometric titrations). 3) Odour, hydrogen sulphide and methyl mercaptan were not removed if sufficient air did not pass with the liquid.
4) Kolonnen mistet effekten etter en tid. 4) The column lost its effect after a while.
Foruten det faktum at lukt, hydrogensulfid og metylmerkaptan lot seg fjerne ved denne metode, viste altså forsokene at det måtte være en luftoksydasjon som fant sted (pkt. 1, 2, 3), og at kolonnematerialet virket inn (pkt.4), dvs. at det var en katalytisk oksydasjon. Apart from the fact that smell, hydrogen sulphide and methylmercaptan could be removed by this method, the experiments showed that there must have been an air oxidation that took place (points 1, 2, 3), and that the column material had an effect (point 4), i.e. .that it was a catalytic oxidation.
Det ble antatt at hydrogensulfid var oksydert til elementært svovel som It was assumed that hydrogen sulphide was oxidized to elemental sulfur which
satt igjen på kolonnematerialet. Denne antagelse ble bekreftet ved at varm hvitlut som ble sendt gjennom kolonne, ble anriket på polysulfid. (Farge gul/orange/rod, avhengig av konsentrasjonen. Bestemt kvantitativt ved potensiometrisk titrering etter overforing til ekvivalent mengde tiosulfat ved hjelp av natrium sulfitt. ) Det er kjent at elementært svovel loses i sulfidlosninger, som f. eks. hvitlut og gronnlut. Forsoket viste dermed også at sulfatprosessen selv har kjemikalier som kan anvendes for å befri kolonnematerialet for det svovel som avsettes. left on the column material. This assumption was confirmed by the fact that hot white liquor sent through the column was enriched in polysulphide. (Colour yellow/orange/red, depending on the concentration. Determined quantitatively by potentiometric titration after conversion to an equivalent amount of thiosulphate using sodium sulphite. ) It is known that elemental sulfur dissolves in sulphide solutions, such as e.g. white liquor and green liquor. The experiment thus also showed that the sulphate process itself has chemicals that can be used to rid the column material of the sulfur that is deposited.
Det ubehandlede kondensat inneholdt oljelignende dråper av varierende mengde og dråpestørrelse. Etter å ha passert gjennom kolonnen var kondensatet imidlertid helt klart. Slik oljeavsetning må antas å redusere kolonnematerialets aktive overflate. Dette ble bekreftet ved at kolonnen etter å ha mistet sin effekt, igjen ble effektiv etter behandling med damp ved ca. ]80-190°C. The untreated condensate contained oil-like droplets of varying quantity and droplet size. After passing through the column, however, the condensate was completely clear. Such oil deposition must be assumed to reduce the active surface of the column material. This was confirmed by the fact that the column, after losing its effect, became effective again after treatment with steam at approx. ]80-190°C.
Ved å folge kondensatene en tid fant man at oljemengden kunne variere innen vide grenser. Det ble derfor gjort forsok på å fjerne oljen for kondensatet gikk til kolonnen. Effektiv oljefjerning er oppnådd ved forst å fjerne store dråper ved at disse får anledning til å flyte opp på vannfasen og deretter fjerne de finfordelte, svevende oljedråper fra vannfasen ved hjelp av koalesens. By following the condensates for some time, it was found that the amount of oil could vary within wide limits. An attempt was therefore made to remove the oil because the condensate went to the column. Effective oil removal is achieved by first removing large droplets by allowing them to float on the water phase and then removing the finely divided, floating oil droplets from the water phase by means of coalescence.
Prover av de vannklare kondensater etter koalesensfiltreringen er ekstra-hert med organiske løsningsmidler, og ekstraktene er indersokt ved hjelp av gasskromatografi. Analysene viste at det var tilstede et meget stort antall polare og upolare organiske forbindelser. Tilsvarende analyser av prover tatt etter kolonnegjennomgangen viste at disse forbindelser nærmest ble fullstendig fjernet ved behandlingen. De forbindelser som man fikk frem ved denne analysemetode, ble antatt vesentlig å være de hoyere organiske forbindelser. Da disse, såvel som hydrogensulfid og lavere organiske svovelforbindelser, må kunne forventes å ha en akutt giftvirkning på livet i resipienten, ble kondensatprover benyttet ved studier av dodelighet av lakseyngel. Det ble funnet at de ubehandlede var 3-35 ganger så toksiske som de behandlede. Samples of the water-clear condensates after the coalescence filtration are extracted with organic solvents, and the extracts are analyzed using gas chromatography. The analyzes showed that a very large number of polar and non-polar organic compounds were present. Corresponding analyzes of samples taken after the column review showed that these compounds were almost completely removed by the treatment. The compounds obtained by this method of analysis were thought to be essentially the higher organic compounds. As these, as well as hydrogen sulphide and lower organic sulfur compounds, must be expected to have an acute toxic effect on life in the recipient, condensate samples were used in studies of the mortality of salmon fry. It was found that the untreated ones were 3-35 times as toxic as the treated ones.
Toksisitetsforsokene (96 timer - LC50) ble utfort ved Norsk institutt for vannforskning (NIVA). De gasskromatografiske undersøkelser ble utfort ved Sentralinstitutt for industriell forskning (SI) ved hjelp avbl.a. glas ska pi Ilar-kolonne og flammeionisasjonsdetektor . Innholdet av la vtkokende organiske forbindelser, som f. eks. metanol, er studert ved PFI ved hjelp av en gasskromatograf med polyalkylenglykol-kolonne og varmetrådsdetektor. The toxicity tests (96 hours - LC50) were carried out at the Norwegian Institute for Water Research (NIVA). The gas chromatographic investigations were carried out at the Central Institute for Industrial Research (SI) with the help of, among others, glass ska pi Ilar column and flame ionization detector . The content of low-boiling organic compounds, such as methanol, has been studied at PFI using a gas chromatograph with a polyalkylene glycol column and hot wire detector.
Foruten metanol finner man spor av én annen forbindelse (anslått til under 1,5% av metanolmengden). Dette tyder på at metanol i praksis bor kunne anrikes fra de rensede kondensater uten for store krav til fraksjonert separasjon. Lukt studier ved hjelp av head-space-teknikk viste reduksjon i antall og totalinnhold av avgående luktstoffer ved 40°C (SI). Besides methanol, traces of one other compound are found (estimated at less than 1.5% of the methanol amount). This suggests that methanol could in practice be enriched from the purified condensates without excessive requirements for fractional separation. Odor studies using the head-space technique showed a reduction in the number and total content of outgoing odorants at 40°C (SI).
Det f or soksanlegg som er benyttet, er vist i over siktstegning. Detts opp-bygging er som folger: Ved hjelp av ventiler (l, 2) og pumper (Pl, P2) tas det ut en delstrom fra kondensatledningen (i eks. på tegningen tas denne fra inndampingsstasjonens avlop). Evt. faste partikler og storre oljedråpef fraskilles i et forfilter (3) med overlop (4). Koalesensenheten består av to parallellkoblede koalesens-filterpatroner (5) av type Balston. Oksydasjonen utfores i en 4 m stål-kolonne med 8 liter katalysatormas se. Kolonnen har tilfor sel av kondensat (alternativt hvitlut for fjerning av utfelt svovel) via pumpe (P3) og mengde-måler (9), trykkluft via måler (18) samt damp for regenerering. The control system used is shown in the overhead view. Its construction is as follows: With the help of valves (l, 2) and pumps (Pl, P2), a partial flow is taken from the condensate line (in the example in the drawing this is taken from the evaporation station's drain). Any solid particles and larger oil droplets are separated in a pre-filter (3) with overflow (4). The coalescence unit consists of two parallel-connected coalescence filter cartridges (5) of the Balston type. The oxidation is carried out in a 4 m steel column with 8 liters of catalyst mass. The column is supplied with condensate (alternatively white liquor for removing precipitated sulphur) via pump (P3) and quantity meter (9), compressed air via meter (18) and steam for regeneration.
Kolonnens effektivitet overvåkes ved en H^S -detektor montert under lokket The efficiency of the column is monitored by an H^S detector mounted under the lid
i oppsamlingsbeholderen, og ytterligere kontroll får man ved å ta ut prover for luktbedommelse og for potensiometrisk titrering av I^S og CH^SH. in the collection container, and further control is obtained by taking samples for odor assessment and for potentiometric titration of I^S and CH^SH.
Studie av oksydasjonsko1onnens virkningsgrad Study of the efficiency of the oxidation chain
Kolonnemateriale: Aktivt kull, 8 liter, kornstdrrelse 0,5 - 2,5 mm Type: Lurgi Hydraffin LS supra Column material: Activated carbon, 8 litres, grain size 0.5 - 2.5 mm Type: Lurgi Hydraffin LS supra
Anm. : Innledende forsok utfort med bl. a. vanlig aktivt kull uten tekniske spesifikasjoner, innkjopt fra forretning i Oslo, gav tilsvarende resultater m.h.p. lukt, H2S og CH-jSH. Note : Initial trial carried out with a. ordinary activated carbon without technical specifications, purchased from a business in Oslo, gave similar results with regard to smell, H2S and CH-jSH.
Kolonne fylt 2.10.79 Column filled 2.10.79
Forsok utfort 2. 10. -4. 10. 79: INNDAMPNINGSKONDENSAT Try out 2. 10. -4. 10. 79: EVAPORATION CONDENSATE
Inngående kondensat: Incoming condensate:
Utgående kondensat: Outgoing condensate:
Fjernet i alt H^S + CH3SH tilsvarende 360 g S A total of H^S + CH3SH removed corresponding to 360 g of S
Regenerert med ca. 5 kg damp (190°C, 13 kg/cm^) Regenerated with approx. 5 kg of steam (190°C, 13 kg/cm^)
forts. 15. 10. -17. 10. continued 15. 10. -17. 10.
Inngående kondensat: Incoming condensate:
Utgående kondensat: Outgoing condensate:
Fjernet i alt H2S + CH3SH tilsvarende 23 0 g S forts. 22. 1. 0 - 25. 10. Removed in total H2S + CH3SH corresponding to 23 0 g S cont. 22. 1. 0 - 25. 10.
Fjernet i alt H2S + CHjSH tilsvarende 310 gS Removed in total H2S + CHjSH corresponding to 310 gS
Kondensatmengde etter forrige dampregenerering: 350 1 + 600 1 = 950 1 Condensate quantity after previous steam regeneration: 350 1 + 600 1 = 950 1
" " totalt: 720 1 + 950 1 = 1470 1 " " total: 720 1 + 950 1 = 1470 1
Fjernet H^S + CH3SH totalt tilsvarende 540 g S Removed H^S + CH3SH in total corresponding to 540 g S
Regenerert med ca. 6 kg damp (190°C, 12, 8 kg/cm^) Regenerated with approx. 6 kg of steam (190°C, 12.8 kg/cm^)
Regenerert med ca. 4,5 1 varm hvitlut, 30 min. Regenerated with approx. 4.5 1 hot white vinegar, 30 min.
Drenert polysulfidholdig lut. Vasket med ca. 40 liter vann Drained polysulphide-containing lye. Washed with approx. 40 liters of water
forts. 25.2. - 27.2.80 continued 25.2. - 27.2.80
Fjernet i alt H2S + CH3SH tilsvarende 230 g/S A total of H2S + CH3SH removed corresponding to 230 g/S
forts. 4.3. continued 4.3.
Fjernet i alt H2S + CH3SH tilsvarende 33 0 g/ S Removed in total H2S + CH3SH corresponding to 33 0 g/ S
560 g/ S 560 g/S
Forsøksserien avsluttet etter behandling av i alt 2270 1 ur ens et inndampnings - kondensat ved fjerning av H2S + CH-jSH tilsvarende 1430 g svovel. The test series ended after treating a total of 2270 1 hours of an evaporation condensate by removing H2S + CH-jSH corresponding to 1430 g of sulphur.
Forsok utfort 28. 5. - 9.10.80: KOKERIKONDENSAT Trial continued 28. 5. - 9.10.80: COOKER CONDENSATE
Kolonnemateriale som ovenfor Column material as above
Kolonne fylt 21.5. Column filled 21.5.
Inngående kondensat: Incoming condensate:
Utgående kondensat: Outgoing condensate:
Forsdket avsluttet, kolonnen fortsatt effektiv. Research concluded, the column still effective.
G a s s k r o m a t og r a f i s k e analyser (utfort på SI) G a s s ch r o m a t a n d r a p h i c a l a y s (continued on SI)
Ekstraksjon med cyklohexan omfatter upolare forbindelser, etterfulgt av surgjoring og ekstraksjon med butyl-acetat og derivatisert med et trimetyl-silylreagens for bestemmelse av de mer polare forbindelser. De forste studert på glasskapillarkolonne, de andre på fylt kolonne, begge med flamm eionisasjonsdetektor. Extraction with cyclohexane involves non-polar compounds, followed by acidification and extraction with butyl acetate and derivatization with a trimethylsilyl reagent to determine the more polar compounds. The first studied on a glass capillary column, the others on a packed column, both with a flame ionization detector.
Inndampnings kondensat fra 17. 10.79. Evaporation condensate from 17. 10.79.
Mengden av både de upolare og de polare forbindelser var meget sterkt redusert etter kondensatbehandlingen i oksydasjonskolonnen. Hovedkomponenten av de upolare forbindelser var redusert ca. 20 000 ganger (fra 60 ppm til 3 • 10 _3ppm). For de polare forbindelser ble det funnet en reduksjon på ca. 600 ganger for hovedkomponenten. The quantity of both the non-polar and the polar compounds was greatly reduced after the condensate treatment in the oxidation column. The main component of the non-polar compounds was reduced approx. 20,000 times (from 60 ppm to 3 • 10 _3ppm). For the polar compounds, a reduction of approx. 600 times for the main component.
Kokerikondensat fra primo juni 1980 Boiler condensate from early June 1980
For de upolare forbindelser fant man en reduksjon på ca. 160 ganger. For the non-polar compounds, a reduction of approx. 160 times.
I den polare fraksjon ble det ikke påvist noen forbindelser i proven tatt In the polar fraction, no compounds were detected in the sample taken
etter oksydas jonskolonnen, hvilket tilsvarer minst 200 gangers reduksjon når deteksjons grens en legges til grunn. after the oxidase ion column, which corresponds to at least a 200-fold reduction when a detection limit is taken into account.
Luktanalyser ved head-space-teknikk (utfort ved SI) Odor analyzes by head-space technique (continued at SI)
Inndampningskoiidensatproven fra for og etter oksydasjonskolonnen ble varmet 1 time ved 40°C og gassen over væsken (head-space) dradd ut, konsentrert på aktivt kull og analysert i gasskromatograf. Det oppgis at det var meget stor forskjell på provene, idet ca. halvparten av for-bindelsene fra proven for oksydasjonen er borte i den fra etter oksydasjonen. Totalinnholdet er ca. 4 ganger storre i den ubehandlede. Noen få nye flyktige forbindelser ser ut til å dannes, men disse er tilstede i svært liten mengde. Det synes vesentlig å være dim ety Idi sulfid. The evaporation coiidensate sample from before and after the oxidation column was heated for 1 hour at 40°C and the gas above the liquid (head-space) extracted, concentrated on activated carbon and analyzed in a gas chromatograph. It is stated that there was a very large difference between the samples, as approx. half of the compounds from the sample before the oxidation are gone in the one from after the oxidation. The total content is approx. 4 times larger in the untreated. A few new volatile compounds appear to form, but these are present in very small amounts. It seems essential to be dim ety Idi sulphide.
Avdriving av metanol og studie av dennes renhet Extraction of methanol and study of its purity
Metanol ble avdestillert (utgjorde ca. 5 g/l) og analysert på PFI's gasskromatograf. Kromatogrammene viste bare spor av én forbindelse utenom metanol, og mengden av denne ble anslått til under 1,5 % av metanolmengden. Methanol was distilled off (amounting to approx. 5 g/l) and analyzed on PFI's gas chromatograph. The chromatograms showed only traces of one compound other than methanol, and the amount of this was estimated to be less than 1.5% of the methanol amount.
Koales ens Koalas alike
At koalesensfiltrering var effektivt ble vist ved at 1) det samlet seg "olje" That coalescence filtration was effective was shown by the fact that 1) "oil" accumulated
i toppen av enheten, og 2) kondensatet var ofte blakket foran enheten og klart etter. Oljeinnholdet i ubehandlet kondensat varierer innen meget vide grenser. at the top of the unit, and 2) the condensate was often cloudy before the unit and clear after. The oil content in untreated condensate varies within very wide limits.
LITTERATUR LITERATURE
1) Kirk Othmer: 1) Kirk Othmer:
Encyclopedia of Chem. Techn. Encyclopedia of Chem. Technology
3. utg. , vol. 4, s. 77-80 - Cellulose Preparation 3rd ed. , vol. 4, pp. 77-80 - Cellulose Preparation
1. " " 11, s.262-265 - Pulp. Sulfate Process 1. " " 11, p.262-265 - Pulp. Sulfate Process
2) Pulp and Paper: 2) Pulp and Paper:
Chemistry and Chem. Techn. Ed.: J. P. Casey, 1980 Chemistry and Chem. Technology Ed.: J.P. Casey, 1980
a) 3. utg. , vol. 1, s. 475-76 - Treatment of Digester and Evaporator Condensates b) 3. " " 2, s. 1228-1229 - Kraft Mill Process Modifications 3) Vettenranta, I.: Enso-Biox Method. A Biological Method for Purifying Kraft Pulp Mill Condensates a) 3rd ed. , vol. 1, pp. 475-76 - Treatment of Digester and Evaporator Condensates b) 3. " " 2, pp. 1228-1229 - Kraft Mill Process Modifications 3) Vettenranta, I.: Enso-Biox Method. A Biological Method for Purifying Kraft Pulp Mill Condensates
1 976 Intern. Environmental Improvement Conference 1 976 Internal. Environmental Improvement Conference
Montreal 6.-8. okt. 1976 Montreal 6-8 increased. 1976
(Henviser til O. Koistinen, finsk patent 46497 av april 1973) (Refers to O. Koistinen, Finnish patent 46497 of April 1973)
4) Smith, G.C. & Knowles, S.E. & Green, R.P.: (The Mead Corp. ) Polysulfide Liquor Generation with MOXY System I 4) Smith, G.C. & Knowles, S.E. & Green, R.P.: (The Mead Corp. ) Polysulfide Liquor Generation with MOXY System I
1974 TAPPI Alkaline Pulping Conference, 1974 TAPPI Alkaline Pulping Conference,
Seattle 16. -18. sept. 1974 Seattle 16.-18. Sept. 1974
5) Norsk pat.nr. 102 304 (innvilget 8. juni 1963) 5) Norwegian patent no. 102,304 (granted June 8, 1963)
Claims (2)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO811259A NO150971C (en) | 1981-04-10 | 1981-04-10 | PROCEDURE FOR CLEANING OF CONDENSATIVES FROM THE SULPHATE PROCESS |
| SE8202251A SE462169B (en) | 1981-04-10 | 1982-04-07 | PROCEDURE FOR CLEANING OF CONDENSATED FROM THE SULPHATE PROCESS |
| CA000400790A CA1205930A (en) | 1981-04-10 | 1982-04-08 | Method for the purification of condensates from the sulfate process |
| FI821271A FI73254C (en) | 1981-04-10 | 1982-04-08 | FOERFARANDE FOER RENING AV SULFATPROCESSENS KONDENSATER. |
| JP57058998A JPS57180484A (en) | 1981-04-10 | 1982-04-10 | Method of purifying condensed liquid generated through sulfate method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO811259A NO150971C (en) | 1981-04-10 | 1981-04-10 | PROCEDURE FOR CLEANING OF CONDENSATIVES FROM THE SULPHATE PROCESS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO811259L NO811259L (en) | 1982-10-11 |
| NO150971B true NO150971B (en) | 1984-10-08 |
| NO150971C NO150971C (en) | 1985-01-23 |
Family
ID=19886021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO811259A NO150971C (en) | 1981-04-10 | 1981-04-10 | PROCEDURE FOR CLEANING OF CONDENSATIVES FROM THE SULPHATE PROCESS |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS57180484A (en) |
| CA (1) | CA1205930A (en) |
| FI (1) | FI73254C (en) |
| NO (1) | NO150971C (en) |
| SE (1) | SE462169B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE9403818L (en) * | 1994-11-08 | 1996-05-09 | Kvaerner Pulping Tech | Method of ozone bleaching |
| FI128221B (en) | 2015-04-27 | 2019-12-31 | Metsae Fibre Oy | Method for regenerating a catalyst used for producing polysulphide lye |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA737730B (en) * | 1972-10-26 | 1974-09-25 | St Regis Paper Co | Process for reducing the organic carbon content and improving the color of aqueous plant effluents |
| JPS5066480A (en) * | 1973-10-18 | 1975-06-04 | ||
| JPS562887A (en) * | 1979-06-20 | 1981-01-13 | Toshiba Corp | Treatment of waste alkali washing liquid for deodorizing |
-
1981
- 1981-04-10 NO NO811259A patent/NO150971C/en unknown
-
1982
- 1982-04-07 SE SE8202251A patent/SE462169B/en not_active IP Right Cessation
- 1982-04-08 CA CA000400790A patent/CA1205930A/en not_active Expired
- 1982-04-08 FI FI821271A patent/FI73254C/en not_active IP Right Cessation
- 1982-04-10 JP JP57058998A patent/JPS57180484A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| FI821271L (en) | 1982-10-11 |
| NO811259L (en) | 1982-10-11 |
| FI73254B (en) | 1987-05-29 |
| NO150971C (en) | 1985-01-23 |
| FI821271A0 (en) | 1982-04-08 |
| CA1205930A (en) | 1986-06-10 |
| SE8202251L (en) | 1982-10-11 |
| FI73254C (en) | 1987-09-10 |
| SE462169B (en) | 1990-05-14 |
| JPS57180484A (en) | 1982-11-06 |
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